Hair dyeing compositions

ABSTRACT

Hair dyeing compositions contain N-cycloalkyl-3-aminophenols corresponding to the following formula ##STR1## in which n is an integer of 4 to 8 and R 1 , R 2 , and R 3  independently of one another represent hydrogen, methyl groups or chlorine, 
     or salts thereof as oxidation dye intermediates of the coupler type in addition to typical primary intermediates in a carrier. In conjunction with typical primary intermediates, for example of the p-phenylenediamine derivative type, the new coupler compounds produce shades of brown of high fastness.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to hair dyeing compositions based on oxidationdyes. Hair dyeing compositions of the type in question contain oxidationdye intermediates in a cosmetic carrier. The oxidation dye intermediatesused are primary intermediates and coupler substances which form dyesunder the effect of oxidizing agents or atmospheric oxygen. The cosmeticcarriers used for the oxidation dye intermediates are creams, emulsions,gels, shampoos, foam aerosols or other compositions suitable forapplication to the hair.

2. Statement of Related Art

By virtue of their intense colors and good fastness properties,so-called oxidation dyes, which are formed by the oxidative coupling ofone or more primary intermediate components with one another or with oneor more coupler components, play a prominent part in the dyeing of hair.The primary intermediates used are normally primary aromatic aminescontaining another free or substituted hydroxy or amino group in thepara position or ortho position, diamino-pyridine derivatives,heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives, andtetraaminopyrimidines, while the so-called coupler substances arem-phenylene-diamine derivatives, naphthols, resorcinol derivatives andpyrazolones.

Good oxidation dye intermediates have to satisfy above all the followingrequirements: they must form the required shades with sufficientintensity during the oxidative coupling reaction. In addition, they mustbe readily absorbed by human hair without excessively staining thescalp. Dye absorption should also be uniform, i.e. the more heavilystressed ends should not be dyed to a greater extent than the lessdamaged hair roots. The hair colors produced with them should be highlystable to heat, light, and the chemicals used in the permanent waving ofhair. Finally, the oxidation hair dye intermediates should be safe touse from the toxicological and dermatological viewpoint.

3-Aminophenols are already known as oxidation dye intermediates, forexample from DE-AS 11 43 605, DE-AS 11 51 900, DE 24 47 017 C2 and DE 3016 882 Al. However, the hair dyeing compositions produced with theseproducts and known primary intermediate components are unsatisfactorywith regard to the fastness properties of the hair colors obtained withthem. In particular, it is not possible with the known 3-aminophenols toobtain browns of satisfactory naturalness, brilliance, and depth ofcolor.

DESCRIPTION OF THE INVENTION

It has been found that these requirements are satisfied to a high degreeby hair dyeing compositions containing oxidation dye intermediates in acarrier which contain as oxidation dye intermediatesN-cycloalkyl-3-aminophenols corresponding to formula (I): ##STR2## whichn is an integer of 4 to 8 and R¹, R² and R³ independently of one anotherrepresent hydrogen, methyl groups or chlorine, or salts thereof ascoupler components and the primary intermediate components typicallyused in oxidation hair dyes.

N-Cycloalkyl-3-aminophenols corresponding to formula I in which R¹, R²and R³ represent hydrogen and the group ##STR3## is a cyclopentyl orcyclohexyl group optionally substituted by 1 or 2 methyl groups, arepreferred, particularly by virtue of their ready accessibility. Thecompounds mentioned as examples (coupler components C1, C2 and C3) areparticularly preferred.

The N-cycloalkyl-3-aminophenols corresponding to formula I, in which R¹,R² and R³ represent hydrogen, are compounds known from the literature.Their production is known, for example, from EP 181 505 Al. The otherN-cycloalkyl-3-aminophenols corresponding to formula I, in which R¹, R²and R³ represent methyl groups or chlorine, may be similarly obtained bythe process described therein from the corresponding aminophenol and acycloalkanone in the presence of a reducing agent in accordance with thefollowing formula scheme: ##STR4##

In addition to 3 aminophenol, suitable aminophenols are, for example,5-chloro-3-aminophenol, 5-chloro-6-methyl-3-aminophenol,4-chloro-3-aminophenol, 5-methyl-3-aminophenol, 6-methyl-3-aminophenol,2-methyl-6-aminophenol and 2,6-dimethyl-3-aminophenol. Suitablecycloalkanones are, for example, cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 3-methyl cyclohexanone, dimethylcyclopentanone, dimethyl cyclohexanones, isopropyl methyl cyclohexanone,trimethyl cyclopentanones and trimethyl cyclohexanones orcycloheptanone.

The N-cycloalkyl-3-aminophenols corresponding to formula I are valuablecoupler compounds which, in conjunction with a number of typical primaryintermediate components, form intensive oxidation colors having highstability to light, heat, and cold waving, mainly in shades of brown toblue-violet.

Suitable primary intermediates are any of the known compounds such as,for example, p-phenylenediamine, p-tolylenediamine,N,N-diethyl-2-methyl-p-phenylenediamine,N-ethyl-N-(2-hydroxyethyl)-p-phenylenediamine,chloro-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,N,N-dimethyl-p-phenylenediamine, methoxy-p-phenylenediamine,2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine,2-chloro-6-methyl-p-phenylenediamine,6-methoxy-3-methyl-p-phenylenediamine, 2,5-diaminoanisole,N-(2-hydroxypropyl)-p-phenylenediamine,N-2-methoxyethyl-p-phenylenediamine,N-butyl-N-sulfobutyl-p-phenylenediamine and other compounds of the typementioned which, in addition, may contain one or more NH₂ groups, NHRgroups, NR₂ groups, where R is a C₁₋₄ alkyl radical or a C₂₋₄hydroxyalkyl radical; also p-aminophenols, diamino-pyridine derivativesand, in particular, tetraaminopyrimidines, such as2,4,5,6-tetraaminopyrimidine, 4,5-diamino-2,6-bis-methylaminopyrimidine,2,5-diamino-4-diethylamino-6-methylaminopyrimidine,2,4,5-triamino-6-piperidinopyrimidine,2,4,5-triamino-6-anilinopyrimidine,2,4,5-triamino-6-morpholinopyrimidine,2,4,5-triamino-6-(2-hydroxyethyl)-aminopyrimidine.

Preferred primary intermediate components are p-phenylenediamine,p-tolylenediamine or derivatives of these compounds or salts thereof.

The N-cycloalkyl-3-aminophenols of formula I to be used in accordancewith the invention and the p-phenylenediamine or p-tolylenediaminederivatives suitable as primary intermediate components are be usedeither as such or in the form of their salts with inorganic or organicacids, for example as chloride, sulfate, phosphate, acetate, propionate,lactate, or citrate.

In addition to the N-cycloalkyl-3-aminophenols corresponding to formula(I), the hair-dyeing compositions according to the invention may alsocontain other known couplers which are necessary for modifying theshades and for producing natural hues. Known couplers of the type inquestion include, for example, other m-phenylenediamines, for example2,4-diaminophenyl-2-hydroxyethyl ether, or phenols, resorcinols,m-aminophenols, naphthols, or pyrazolones. Substantive dyes may also beadditionally used for further modifying the shades. Suitable substantivedyes are, for example, nitrophenylenediamines, nitroaminophenols,anthraquinone dyes, or indophenols.

To prepare the hair-dyeing compositions according to the invention, theN-cycloalkyl-3-aminophenols corresponding to formula (I) and the knowncouplers additionally present, if any, are generally used insubstantially molar quantities, based on the primary intermediatecomponents used. Although it has proved best to use molar quantities, acertain excess of individual oxidation dye intermediates is not adisadvantage, so that primary intermediate components and couplercomponents may be present in a molar ratio of from 1 : 0.5 to 1 : 2.

The N-cycloalkyl-3-aminophenols corresponding to formula (I) and theoxidation dye intermediates or substantive dyes otherwise present in thehair dyeing compositions do not have to be individual chemicalcompounds. On the contrary, they may also be mixtures of the coupler orprimary intermediate components to be used in accordance with theinvention.

Basically, the hair color may be oxidatively developed with atmosphericoxygen. However, it is preferred to use a chemical oxidizing agent,particularly when it is desired not only to color, but also to lightenthe hair. Particularly suitable oxidizing agents are hydrogen peroxideor adducts thereof with urea, melamine, or sodium borate and alsomixtures of such hydrogen peroxide adducts with potassiumperoxydisulfate.

To produce the hair-dyeing compositions according to the invention, theoxidation dye intermediates are incorporated into a suitable cosmeticcarrier. Examples of suitable cosmetic carriers are creams, emulsions,gels, or even surfactant-containing foaming solutions, for example,shampoos or other compositions which are suitable for application to thehair. Standard ingredients of cosmetic compositions such as these are,for example, wetting agents and emulsifiers, such as anionic, nonionicor ampholytic surfactants, for example soaps, fatty alcohol sulfates,alkanesulfonates, α-olefin sulfonates, fatty alcohol polyglycol ethersulfates, ethylene oxide adducts with fatty alcohols, fatty acids andalkylphenols, sorbitan fatty acid esters and fatty acid partialglycerides, fatty acid alkanolamides; and thickeners, such as forexample methyl or hydroxyethyl cellulose; starch; fatty components suchas, for example, fatty alcohols, paraffin oils or fatty acid esters;perfume oils; and hair-care additives such as, for example,water-soluble cationic polymers, protein derivatives, pantothenic acid,and cholesterol.

The constituents of the cosmetic carriers are used in the usualquantities in the production of hair dyeing compositions according tothe invention. For example, emulsifiers are used in concentrations of0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% byweight, based on the hair dyeing compositions as a whole.

A particularly suitable carrier is an oil-in-water emulsion containing0.1 to 25% by weight of a fatty component and 0.5 to 30% by weight of anemulsifier from the group of anionic, nonionic, or ampholyticsurfactants.

The oxidation dye intermediates are incorporated into the carrier inquantities of 0.2 to 5% by weight and preferably in quantities of 1 to3% by weight, based on the hair-dyeing composition as a whole. Thecontent of N-cycloalkyl-3-aminophenols corresponding to formula (I) inthe hair dyeing compositions according to the invention may be fromabout 0.05 to 10 millimol per 100 g of the hair dyeing composition.

The hair dyeing compositions according to the invention may be used in amildly acidic, neutral, or alkaline medium, irrespective of the type ofcosmetic composition used, for example a cream, gel, or shampoo. Thehair-dyeing compositions are preferably used at a pH value in the rangefrom 6 to 10 and at temperatures in the range from 15° C. to 40° C.After a contact time of about 30 minutes, the hair-dyeing composition isremoved by rinsing from the hair to be dyed. The hair is then washedwith a mild shampoo and dried. Washing with a shampoo is unnecessarywhen a carrier of high surfactant content, for example a dye shampoo, isused.

The following Examples are intended to illustrate the invention withoutlimiting it in any way.

EXAMPLES

Hair dyeing tests

Hair-dyeing compositions according to the invention were prepared in theform of a cream emulsion having the following composition:

    ______________________________________                                        C.sub.12 -C.sub.18 fatty alcohol                                                                    10.0 g                                                  C.sub.12 -C.sub.14 fatty alcohol + 2 EO sulfate,                                                    25.0 g                                                  Na salt, 28%                                                                  Water                 60.0 g                                                  Primary intermediate (component E)                                                                  7.5 mmol                                                Coupler (component C) 7.5 mmol                                                Na.sub.2 SO.sub.3 (inhibitor)                                                                       1.0 g                                                   Concentrated ammonia solution                                                                       to pH = 9.5                                             Water                 ad 100 g                                                ______________________________________                                    

The constituents were mixed together in the above order. After additionof the oxidation dye intermediates and the inhibitor, the pH value ofthe emulsion was first adjusted to 9.5 with concentrated ammoniasolution, after which the emulsion was made up with water to 100 g.

The hair color was oxidatively developed with 3% hydrogen peroxidesolution as oxidizing agent. To this end, 50 g of hydrogen peroxidesolution (3%) were added to and mixed with 100 g of the emulsion.

The dye cream was applied to approximately 5 cm long strands ofstandardized, 90% grey, but not specially pretreated human hair and leftthereon for 30 minutes at 27° C. After dyeing, the hair was rinsed,washed with a standard shampoo and then dried.

The following N-cycloalkyl-3-aminophenols were used as the couplers(component C):

C1: N-cyclopentyl-3-aminophenol

C2: N-cyclohexyl-3-aminophenol

C3 N-(3-methylcyclohexyl)-3-aminophenol

The following compounds were used as the primary intermediate component(component D):

D1: p-phenylenediamine

D2: p-tolylenediamine

D3: N,N-diethyl-p-phenylenediamine

D4: N,N-bis-(δ-hydroxyethyl)-p-phenylenediamine

D5: N-(δ-hydroxyethyl)-p-phenylenediamine

D6: 2-chloro-p-phenylenediamine

D7: 2,5-diaminobenzyl alcohol

D8: 2-(2,5-diaminophenyl)-ethanol

D9: 1,2-bis-(4-aminophenyl)-ethylenediamine

D10: 2,5-diaminophenyl-δ-ethoxyethyl ether

D11: p-aminophenol

D12: 2,4,5,6-tetraaminopyrimidine

D13: 2-dimethylamino-4,5,6-triaminopyrimidine

The hair colors obtained with these oxidation dye intermediates in thecombinations listed in Table 1 are shown in that Table.

                  TABLE 1                                                         ______________________________________                                                 Primary In- Coupler                                                  Example No.                                                                            termediate  Component Shade Obtained                                 ______________________________________                                        1        D1          C1        Aubergine                                      2        D2          C1        Brown-black                                    3        D3          C1        Black-blue                                     4        D4          C1        Black-blue                                     5        D5          C1        Dark violet                                    6        D6          C1        Dark brown                                     7        D8          C1        Grey-brown                                     8         D11        C1        Brown                                          9         D12        C1        Blue-violet                                    10        D13        C1        Blue-grey                                      11       D2          C2        Brown-black                                    12        D12        C2        Dark violet                                    13       D7          C3        Grey-brown                                     14       D9          C3        Grey-brown                                     15        D10        C3        Dark-violet                                    ______________________________________                                    

What is claimed is:
 1. Hair dyeing compositions comprising a carrierwhich is suitable for application to the hair and:(A)N-cycloalkyl-3-aminophenols or salts thereof, saidN-cycloalkyl-3-aminophenols corresponding to the formula ##STR5## inwhich n is an integer of 4 to 8 and R¹, R², and R³ independently of oneanother represent hydrogen, methyl groups or chlorine as couplercomponents; and (B) primary intermediate components.
 2. Hair dyeingcompositions as claimed in claim 1, wherein R¹, R², and R³ representhydrogen and the moietyis selected from the group consisting ofcyclopentyl, cyclohexyl, methyl cyclopentyl, methyl cyclohexyl, dimethylcyclopentyl, and dimethyl cyclohexyl.
 3. Hair dyeing compositions asclaimed in claim 2, comprising p-phenylenediamine, p-tolylenediamine, orderivatives of these compounds or salts thereof as primary intermediatecomponents.
 4. Hair dyeing compositions as claimed in claim 3,comprising an oil-in-water emulsion containing 0.1 to 25% by weight of afatty component and 0.5 to 30% by weight of an emulsifier from the groupof anionic, nonionic or ampholytic surfactants as carrier and saidN-cycloalkyl-3-aminophenols in a quantity of 0.05 to 10 millimol per 100g of the hair dyeing composition.
 5. Hair dyeing compositions as claimedin claim 1, comprising p-phenylenediamine, p-tolylenediamine, orderivatives of these compounds or salts thereof as primary intermediatecomponents.
 6. Hair dyeing compositions as claimed in claim 5,comprising an oil-in-water emulsion containing 0.1 to 25% by weight of afatty component and 0.5 to 30% by weight of an emulsifier from the groupof anionic, nonionic or ampholytic surfactants as carrier and saidN-cycloalkyl-3-aminophenols in a quantity of 0.05 to 10 millimol per 100g of the hair dyeing composition.
 7. Hair dyeing compositions as claimedin claim 2, comprising an oil-in-water emulsion containing 0.1 to 25% byweight of a fatty component and 0.5 to 30% by weight of an emulsifierfrom the group of anionic, nonionic or ampholytic surfactants as carrierand said N-cycloalkyl-3-aminophenols in a quantity of 0.05 to 10millimol per 100 g of the hair dyeing composition.
 8. Hair dyeingcompositions as claimed in claim 1, comprising an oil-in-water emulsioncontaining 0.1 to 25% by weight of a fatty component and 0.5 to 30% byweight of an emulsifier from the group of anionic, nonionic orampholytic surfactants as carrier and said N-cycloalkyl-3-aminophenolsin a quantity of 0.05 to 10 millimol per 100 g of the hair dyeingcomposition.
 9. Hair dyeing compositions as claimed in claim 8, whereinsaid N-cycloalkyl-3-aminophenols are selected from the group consistingof N-cyclopentyl-3-aminophenol, N-cyclohexyl-3-aminophenol, andN-(3-methylcyclohexyl)-3-aminophenol.
 10. Hair dyeing compositions asclaimed in claim 7, wherein said N-cycloalkyl-3-aminophenols areselected from the group consisting of N-cyclopentyl-3-aminophenol,N-cyclohexyl-3-aminophenol, and N-(3-methylcyclohexyl)-3-aminophenol.11. Hair dyeing compositions as claimed in claim 6, wherein saidN-cycloalkyl-3-aminophenols are selected from the group consisting ofN-cyclopentyl-3-aminophenol, N-cyclohexyl-3-aminophenol, andN-(3-methylcyclohexyl)-3-aminophenol.
 12. Hair dyeing compositions asclaimed in claim 5, wherein said N-cycloalkyl-3-aminophenols areselected from the group consisting of N-cyclopentyl-3-aminophenol,N-cyclohexyl-3-aminophenol, and N-(3-methylcyclohexyl)-3-aminophenol.13. Hair dyeing compositions as claimed in claim 4, wherein saidN-cycloalkyl-3-aminophenols are selected from the group consisting ofN-cyclopentyl-3-aminophenol, N-cyclohexyl-3-aminophenol, andN-(3-methylcyclohexyl)-3-aminophenol.
 14. Hair dyeing compositions asclaimed in claim 3, wherein said N-cycloalkyl-3-aminophenols areselected from the group consisting of N-cyclopentyl-3-aminophenol,N-cyclohexyl-3-aminophenol, and N-(3-methylcyclohexyl)-3-aminophenol.15. Hair dyeing compositions as claimed in claim 2, wherein saidN-cycloalkyl-3-aminophenols are selected from the group consisting ofN-cyclopentyl-3-aminophenol, N-cyclohexyl-3-aminophenol, andN-(3-methylcyclohexyl)-3-aminophenol.
 16. Hair dyeing compositions asclaimed in claim 1, wherein said N-cycloalkyl-3-aminophenols areselected from the group consisting of N-cyclopentyl-3-aminophenol,N-cyclohexyl-3-aminophenol, and N-(3-methylcyclohexyl)-3-aminophenol.